Hydrofluoroether olefins and methods of using same

ABSTRACT

A hydrofluoroether compound represented by the following general formula (I).

FIELD

The present disclosure relates to working fluids that containhydrofluoroether olefins and methods of making and using the same.

BACKGROUND

Various hydrofluoroether olefin compounds are described in, for examplePCT Published Application WO 2010/094019 (Bartelt et al.), and Reactionof Transperfluoropent-2-ene with alcoholates, Kurykin, M. A., German, L.S. Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya (1981), (11),2647-50.

SUMMARY

In some embodiments, a hydrofluoroether compound represented by thefollowing general formula (I) is provided.

(i) Rf₃ is F, Rf₄ is CF₃, and Rf₁ and Rf₂ are independentlyperfluoroalkyl groups (a) having 1 to 2 carbon atoms and optionallycomprising at least one catenated heteroatom, or (b) that are bondedtogether to form a ring structure having 4-8 carbon atoms and optionallycomprising one or more catenated heteroatoms; or (ii) Rf₃ is CF₃, Rf₄ isF, and Rf₁ and Rf₂ are independently perfluoroalkyl groups (a) having 1to 8 carbon atoms and optionally comprising at least one catenatedheteroatom, or (b) that are bonded together to form a ring structurehaving 4 to 8 carbon atoms and optionally comprising one or morecatenated heteroatoms. Rfh is a linear, branched, or cyclic alkyl orfluoroalkyl group of from 1 to 10 carbon atoms that may be saturated orunsaturated and optionally comprises one or more catenated heteroatoms.

In some embodiments, a hydrofluoroether compound represented by thefollowing general formula (II) is provided.

Rf₅ and Rf₆ (i) are each independently perfluoroalkyl groups having 1-8carbon atoms and optionally comprising at least one catenatedheteroatom, or (ii) are bonded together to form a ring structure having4-8 carbon atoms and optionally comprising one or more catenatedheteroatoms. Rfh₁ is a linear, branched, cyclic, or acyclic alkylene orfluoroalkylene group having from 1 to 8 carbon atoms and optionallycomprising one or more catenated heteroatoms. Each of Rf₇, Rf₈, Rf′₇,and Rf′₈ is independently a F or CF₃ group, with the proviso that when:Rf₇ is F, Rf₈ is CF₃, Rf₈ is F, Rf₇ is CF₃, Rf′₇is F, Rf′₈ is CF₃, Rf′₈is F, Rf′₇ is CF₃.

In some embodiments, an apparatus for heat transfer is provided. Theapparatus includes a device and a a mechanism for transferring heat toor from the device. The mechanism comprises a heat transfer fluid thatcomprises a hydrofluoroether compound as described above.

The above summary of the present disclosure is not intended to describeeach embodiment of the present disclosure. The details of one or moreembodiments of the disclosure are also set forth in the descriptionbelow. Other features, objects, and advantages of the disclosure will beapparent from the description and from the claims.

DETAILED DESCRIPTION

In view of an increasing demand for environmentally friendly and loxtoxicity chemical compounds, it is recognized that there exists anongoing need for new working fluids exhibiting further reductions inenvironmental impact and toxicity, and which can meet the performancerequirements of a variety of different applications, and be manufacturedcost-effectively.

As used herein, “catenated heteroatom” means an atom other than carbon(for example, oxygen, nitrogen, or sulfur) that is bonded to at leasttwo carbon atoms in a carbon chain (linear or branched or within a ring)so as to form a carbon-heteroatom-carbon linkage.

As used herein, “fluoro-” (for example, in reference to a group ormoiety, such as in the case of “fluoroalkylene” or “fluoroalkyl” or“fluorocarbon”) or “fluorinated” means only partially fluorinated suchthat there is at least one carbon-bonded hydrogen atom.

As used herein, “perfluoro-” (for example, in reference to a group ormoiety, such as in the case of “perfluoroalkylene” or “perfluoroalkyl”or “perfluorocarbon”) or “perfluorinated” means completely fluorinatedsuch that, except as may be otherwise indicated, there are nocarbon-bonded hydrogen atoms replaceable with fluorine.

As used herein, “substituted” (in reference to a group or moiety) meansthat at least one carbon-bonded hydrogen atom is replaced with a halogenatom. Halogen atoms may include F, Cl, Br, and I.

As used herein, the singular forms “a”, “an”, and “the” include pluralreferents unless the content clearly dictates otherwise. As used in thisspecification and the appended embodiments, the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

As used herein, the recitation of numerical ranges by endpoints includesall numbers subsumed within that range (e.g. 1 to 5 includes 1, 1.5, 2,2.75, 3, 3.8, 4, and 5).

Unless otherwise indicated, all numbers expressing quantities oringredients, measurement of properties and so forth used in thespecification and embodiments are to be understood as being modified inall instances by the term “about.” Accordingly, unless indicated to thecontrary, the numerical parameters set forth in the foregoingspecification and attached listing of embodiments can vary dependingupon the desired properties sought to be obtained by those skilled inthe art utilizing the teachings of the present disclosure. At the veryleast, and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claimed embodiments, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

In some embodiments, the present disclosure is directed tohydrofluoroether olefin compounds represented by the following generalformula (I):

In various embodiments, Rf₃ is F, Rf₄ is CF₃, and Rf₁ and Rf₂ areindependently perfluoroalkyl groups (i) having 1 to 2, 1 or 2 carbonatoms and optionally comprising at least one catenated heteroatom, or(ii) that are bonded together to form a ring structure having 4-8 or 4to 6 carbon atoms and optionally comprising one or more catenatedheteroatoms. In some embodiments, the catenated hereteroatoms of thering structure are selected from oxygen, nitrogen or sulfur

In some embodiments, Rf₃ is CF₃, Rf₄ is F, and Rf1 and Rf₂ areindependently perfluoroalkyl groups (i) having 1 to 8, 1 to 6, or 2 to 5carbon atoms and optionally comprising at least one catenatedheteroatom, or (ii) that are bonded together to form a ring structurehaving 4 to 8 or 4 to 6 carbon atoms and optionally comprising one ormore catenated heteroatoms selected from oxygen, nitrogen or sulfur. Insome embodiments, the catenated hereteroatoms of the ring structure areselected from oxygen and nitrogen.

In some embodiments, Rfh is a linear or branched, cyclic or acyclic,substituted or unsubstituted, monovalent alkyl or fluoroalkyl group offrom 1 to 10, 1 to 6, or 1 to 3 carbon atoms that may be saturated orunsaturated and optionally can contain one or more catenatedheteroatoms.

In some embodiments, the present disclosure is directed tohydrofluoroether olefin compounds represented by the following generalformula (II):

In various embodiments, each Rf₅ and Rf₆ is independently aperfluoroalkyl group having 1 to 8, 1 to 6, or 2 to 5 carbon atoms andoptionally comprises at least one catenated heteroatom. In otherembodiments, adjacent Rf₅ and Rf₆ groups are bonded together to form aring structure having 4 to 8 or 4 to 6 carbon atoms and optionallycomprising one or more catenated heteroatoms. In some embodiments, thecatenated hereteroatoms of the ring structure are selected from oxygenand nitrogen. Each of Rf₇, Rf₈, Rf′₇, and Rf′₈ is independently a F orCF₃ group, with the proviso that when:

Rf₇ is F, Rf₈ is CF₃,

Rf₈ is F, Rf₇ is CF₃,

Rf′₇ is F, Rf′₈ is CF₃,

Rf′₈ is F, Rf′₇ is CF₃.

In various embodiments, Rfh₁ is a linear or branched, cyclic or acyclic,substituted or unsubstituted, divalent alkylene or fluoroalkylene grouphaving from 1 to 8, 2 to 6, or 2 to 4 carbon atoms that is saturated orunsaturated and optionally comprises one or more catenated heteroatoms.

In some embodiments, the Rfh groups may include: —CH₃, —C₂H₅, —C₃H7,—CH₂CH═CH₂, CH₂CCH, —CH₂CH₂OCH₃, —CH₂CF₃, —CH₂C₂F₅, —CH(CF₃)₂, —CH₂C₃F₇,—CH₂CF₂CFHCF₃, —CH(CH₃)CF₂CFHCF₃, —CH₂(CF₂CF₂)_(n)H (where n=1-3),—CH₂CH₂(CF₂)_(x)F (where x=1-8), and

In various embodiments, Rfh₁ groups may include: —CH₂CF₂CF₂CH₂—,—CH₂CH₂CH₂CH₂—, —CH₂CH═CHCH₂—, and —CH₂CH₂OCH₂CH₂—. The hydrogen atomsin Rfh and Rfh₁ can be partially substituted with halogen atoms. Thehalogen atoms may include F, Cl, Br, and I, but are preferably F or Cl,most preferably F.

In some embodiments, the halogen content in the compounds of generalformula (I) and (II) may be sufficient to make the hydrofluoroethernon-flammable according to ASTM D-3278-96 e-1 test method (“Flash Pointof Liquids by Small Scale Closed Cup Apparatus”).

In some embodiments, any of the above discussed O heteroatoms may besecondary O heteroatoms wherein the O is bonded to two carbon atoms. Insome embodiments, any of the above discussed N heteroatoms may betertiary N heteroatoms wherein the N is bonded to three perfluorinatedcarbon atoms. In some embodiments, any of the above discussed Scatenated heteroatoms may be secondary S heteroatoms wherein the S isbonded to two perfluorinated carbon atoms, and the remaining valences onS, if present, are occupied by F.

For purposes of the present disclosure, it is to be appreciated that thehydrofluoroether olefin compounds may include the cis isomer, the transisomer, or a mixture of the cis and trans isomers, irrespective of whatis depicted in a general formula.

In various embodiments, representative examples of the compounds ofgeneral formula (I) include the following:

In illustrative embodiments, representative examples of the compounds ofgeneral formula (II) include the following:

In some embodiments, the hydrofluoroether olefin compounds of thepresent disclosure may be hydrophobic, relatively chemically unreactive,and thermally stable. The hydrofluoroether olefin compounds may have alow environmental impact. In this regard, the hydrofluoroether olefincompounds of the present disclosure may have a global warming potential(GWP) of less 300, 200, 100 or even less than 10. As used herein, GWP isa relative measure of the warming potential of a compound based on thestructure of the compound. The GWP of a compound, as defined by theIntergovernmental Panel on Climate Change (IPCC) in 1990 and updated in2007, is calculated as the warming due to the release of 1 kilogram of acompound relative to the warming due to the release of 1 kilogram of CO2over a specified integration time horizon (ITH).

${{GWP}_{i}( t^{\prime} )} = {\frac{\int_{0}^{ITH}{{a_{i}\lbrack {C(t)} \rbrack}{dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\lbrack {C_{{CO}_{2}}(t)} \rbrack}{dt}}} = \frac{\int_{0}^{ITH}{a_{i}C_{oi}e^{{- t}/\tau_{l}}{dt}}}{\int_{0}^{ITH}{{a_{{CO}_{2}}\lbrack {C_{{CO}_{2}}(t)} \rbrack}{dt}}}}$

In this equation a, is the radiative forcing per unit mass increase of acompound in the atmosphere (the change in the flux of radiation throughthe atmosphere due to the IR absorbance of that compound), C is theatmospheric concentration of a compound, τ is the atmospheric lifetimeof a compound, t is time, and i is the compound of interest. Thecommonly accepted ITH is 100 years representing a compromise betweenshort-term effects (20 years) and longer-term effects (500 years orlonger). The concentration of an organic compound, i, in the atmosphereis assumed to follow pseudo first order kinetics (i.e., exponentialdecay). The concentration of CO₂ over that same time intervalincorporates a more complex model for the exchange and removal of CO₂from the atmosphere (the Bern carbon cycle model).

In some embodiments, the hydrofluoroether olefin compounds of thepresent disclosure can be prepared by electrochemically fluorinating amethyl ester to produce the perfluorinated acyl fluoride. The methylesters can be prepared by well known methods in the literature such asthe Michael reaction of an amine with an alkene such as methylmethacrylate. Once prepared these organics can be made to undergoelectrochemical fluorination by the method described in, for example,U.S. Pat. No. 2,713,593 (Brice et al.) and in R. E. Banks, Preparation,Properties and Industrial Applications of Organofluorine Compounds,pages 19-43, Halsted Press, New York (1982)). Upon isolation, these acidfluorides can be reacted with metal carbonate salts such as potassiumcarbonate and sodium carbonate at elevated temperatures to produce theintermediate perfluoroolefins (i.e., perfluorinated propenyl amines).These intermediate perfluoroolefins can then be reacted with varioushydrocarbon or fluorinated alcohols in the presence of a base andoptionally an organic solvent to produce the compounds of the presentdisclosure.

The nitrogen-containing hydrofluoroether olefin of the presentdisclosure can be conveniently prepared in high yield by the addition ofan alcohol to a perfluorinated propenyl amine in the presence of asuitable base, as illustrated in Scheme 1.

Generally this reaction produces the desired hydrofluoroether (HFE)olefin of the present disclosure as the major product, althoughrelatively small amounts of the corresponding HFE-Hydride byproduct canbe produced as well. The HFE-Hydride byproduct, if formed, is readilyconverted to the desired HFE-Olefin by post-treatment with a strongbase, such as KOH or a salt of t-butoxide, ultimately producing highyields of the desired and relatively pure HFE-Olefin product.

The alcohol addition reaction illustrated in Scheme 1 can be effected bycombining the perfluorinated propenyl amine starting compound and thestarting alcohol in the presence of at least one base (for example, aLewis base). Useful bases include potassium carbonate, cesium carbonate,potassium fluoride, potassium hydroxide, potassium methoxide,triethylamine, trimethylamine, potassium cyanate, potassium bicarbonate,sodium carbonate, sodium bicarbonate, sodium methoxide, cesium fluoride,lithium t-butoxide, potassium t-butoxide, and the like, and mixturesthereof; with potassium carbonate, potassium hydroxide, and mixturesthereof being preferred. A metal salt of the starting alcohol reagentcan also be used as the base.

The reactants and base can be combined in a reactor (for example, aglass reactor or a metal pressure reactor) in any order, and thereaction can be run at a desired temperature (for example, from about 0°C. to about 75° C.) under the above described conditions with agitation.Generally, however, use of a non-reactive, aprotic organic solvent (forexample, acetonitrile, acetone, tetrahydrofuran, glyme, or a mixture oftwo or more thereof) can facilitate the reaction. The resulting productcan be purified by, for example, distillation. HFE-Hydride reactionby-products can be removed (or converted to desired product) by reactionwith a strong base or a good HF scavenger that will preferentiallydehydrofluorinate the HFE-Hydride. Strong bases suitable for thispurpose include, for example, potassium hydroxide, potassium t-butoxide,lithium t-butoxide, lithium diisopropylamide, DBU and the like. Thesebases can be used with or without a solvent or a phase transfercatalyst.

The perfluorinated propenyl amine starting compounds can be prepared bystandard synthetic procedures that are well known in the art, includingthose described by Abe in JP 01070444A and JP 0107445A, which areincorporated herein by reference in their entirety.

Representative examples of perfluorinated propenyl amines useful asstarting compounds for preparing the nitrogen-containing HFE-Olefincompositions of this disclosure include, for example, 1- and 2-propenylamines, shown in FIGS. 1 and 2, respectively. Although the structures inFIG. 1 are all shown as trans isomers, the corresponding cis isomers areequally useful starting compounds. Typically the cis and transperfluorinated 1-propenyl amine starting compounds of FIG. 1 are madeand used as a mixture of cis and trans isomers.

Note: The 1-propenyl amines in FIG. 1, above, can be cis or transisomers or a mixture thereof, although only the trans isomers are shown.

Alcohols useful as starting compounds for preparing the HFE-Olefincompositions of this disclosure can be monofunctional or polyfunctionalalcohols. In one embodiment the alcohols are monofunctional. In anotherembodiment, the alcohols are difunctional.

Useful alcohols are generally commercially available or readily preparedand provide the desired HFE-Olefin product in high yield. In someembodiments, hydrocarbon alcohols may be employed due to theirrelatively lower cost (in comparison with fluorocarbon alcohols). Insome embodiments, suitable alcohols are generally those that provideHFE-Olefin products that are non-flammable. In this regard,mono-functional hydrocarbon alcohols having no more than six carbonatoms or three carbon atoms may be useful.

Representative examples of suitable alcohols include, for example,methanol, ethanol, propanol, butanol, 2-methoxyethanol,tetrahydrofurfuryl alcohol, 1,4-butanediol, 2-butene-1,4-diol,diethyleneglycol, (CH₃)₂NC₂H₄OH, CF₃CH₂OH, C₂F₅CH₂OH, C₃F₇CH₂OH,(CF₃)₂CHOH, HCF₂CF₂CH₂OH, H(CF₂CF₂)₂CH₂OH, H(CF₂CF₂)₃CH₂OH,CF₃CFHCF₂CH₂OH, CF₃CFHCF₂CH(CH₃)OH, C₄F₉CH₂CH₂OH, C₆F₁₃CH₂CH₂OH,C₈F₁₇CH₂CH₂OH, C₄F₉OCH₂CH₂OH, HOCH₂CF₂CF₂CH₂OH, or the like.

In some embodiments, the alcohols include methanol, ethanol, 1-propanol,2-methoxyethanol, 1,4-butanediol, 2-butene-1,4-diol, diethylene glycol,CF₃CH₂OH, HCF₂CF₂CH₂OH, H(CF₂CF₂)₂CH₂OH, CF₃CFHCF₂CH₂OH,CF₃CFHCF₂CH(CH₃)OH, C₄F₉CH₂CH₂OH and HOCH₂CF₂CF₂CH₂OH.

In some embodiments, the present disclosure is further directed toworking fluids that include the above-described hydrofluoroethercompounds as a major component. For example, the working fluids mayinclude at least 25%, at least 50%, at least 70%, at least 80%, at least90%, at least 95%, or at least 99% by weight of the above-describedhydrofluoroether compounds based on the total weight of the workingfluid. In addition to the hydrofluoroether compounds, the working fluidsmay include a total of up to 75%, up to 50%, up to 30%, up to 20%, up to10%, or up to 5% by weight of one or more of the following components:alcohols, ethers, alkanes, alkenes, perfluorocarbons, perfluorinatedtertiary amines, perfluoroethers, cycloalkanes, esters, ketones,oxiranes, aromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, hydrofluoroolefins,hydrochlorofluoroolefins, hydrofluoroethers, or mixtures thereof, basedon the total weight of the working fluid. Such additional components canbe chosen to modify or enhance the properties of a composition for aparticular use.

In some embodiments, the present disclosure is further directed to anapparatus for heat transfer that includes a device and a mechanism fortransferring heat to or from the device. The mechanism for transferringheat may include a heat transfer working fluid that includes ahydrofluoroether compound of the present disclosure.

The provided apparatus for heat transfer may include a device. Thedevice may be a component, work-piece, assembly, etc. to be cooled,heated or maintained at a predetermined temperature or temperaturerange. Such devices include electrical components, mechanical componentsand optical components. Examples of devices of the present disclosureinclude, but are not limited to microprocessors, wafers used tomanufacture semiconductor devices, power control semiconductors,electrical distribution switch gear, power transformers, circuit boards,multi-chip modules, packaged and unpackaged semiconductor devices,lasers, chemical reactors, fuel cells, and electrochemical cells. Insome embodiments, the device can include a chiller, a heater, or acombination thereof.

In yet other embodiments, the devices can include electronic devices,such as processors, including microprocessors. As these electronicdevices become more powerful, the amount of heat generated per unit timeincreases. Therefore, the mechanism of heat transfer plays an importantrole in processor performance. The heat-transfer fluid typically hasgood heat transfer performance, good electrical compatibility (even ifused in “indirect contact” applications such as those employing coldplates), as well as low toxicity, low (or non-) flammability and lowenvironmental impact. Good electrical compatibility suggests that theheat-transfer fluid candidate exhibit high dielectric strength, highvolume resistivity, and poor solvency for polar materials. Additionally,the heat-transfer fluid should exhibit good mechanical compatibility,that is, it should not affect typical materials of construction in anadverse manner.

The provided apparatus may include a mechanism for transferring heat.The mechanism may include a heat transfer fluid. The heat transfer fluidmay include one or more hydrofluoroether compounds of the presentdisclosure. Heat may be transferred by placing the heat transfermechanism in thermal contact with the device. The heat transfermechanism, when placed in thermal contact with the device, removes heatfrom the device or provides heat to the device, or maintains the deviceat a selected temperature or temperature range. The direction of heatflow (from device or to device) is determined by the relativetemperature difference between the device and the heat transfermechanism.

The heat transfer mechanism may include facilities for managing theheat-transfer fluid, including, but not limited to pumps, valves, fluidcontainment systems, pressure control systems, condensers, heatexchangers, heat sources, heat sinks, refrigeration systems, activetemperature control systems, and passive temperature control systems.Examples of suitable heat transfer mechanisms include, but are notlimited to, temperature controlled wafer chucks in plasma enhancedchemical vapor deposition (PECVD) tools, temperature-controlled testheads for die performance testing, temperature-controlled work zoneswithin semiconductor process equipment, thermal shock test bath liquidreservoirs, and constant temperature baths. In some systems, such asetchers, ashers, PECVD chambers, vapor phase soldering devices, andthermal shock testers, the upper desired operating temperature may be ashigh as 170° C., as high as 200° C., or even as high as 230° C.

Heat can be transferred by placing the heat transfer mechanism inthermal contact with the device. The heat transfer mechanism, whenplaced in thermal contact with the device, removes heat from the deviceor provides heat to the device, or maintains the device at a selectedtemperature or temperature range. The direction of heat flow (fromdevice or to device) is determined by the relative temperaturedifference between the device and the heat transfer mechanism. Theprovided apparatus can also include refrigeration systems, coolingsystems, testing equipment and machining equipment. In some embodiments,the provided apparatus can be a constant temperature bath or a thermalshock test bath.

In some embodiments, the present disclosure is directed to a fireextinguishing composition. The composition may include one or morehydrofluoroether compound of the present disclosure and one or moreco-extinguishing agents.

In illustrative embodiments, the co-extinguishing agent may includehydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,hydrobromocarbons, iodofluorocarbons, fluorinated ketones,hydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,iodofluorocarbons, hydrobromofluorocarbons, fluorinated ketones,hydrobromocarbons, fluorinated olefins, hydrofluoroolefins, fluorinatedsulfones, fluorinated vinylethers, unsaturated fluoro-ethers,bromofluoroolefins, chlorofluorolefins, iodofluoroolefins , fluorinatedvinyl amines, fluorinated aminopropenes and mixtures thereof.

Such co-extinguishing agents can be chosen to enhance the extinguishingcapabilities or modify the physical properties (e.g., modify the rate ofintroduction by serving as a propellant) of an extinguishing compositionfor a particular type (or size or location) of fire and can preferablybe utilized in ratios (of co-extinguishing agent to hydrofluoroethercompound) such that the resulting composition does not form flammablemixtures in air.

In some embodiments, the hydrofluoroether compounds and theco-extinguishing agent may be present in the fire extinguishingcomposition in amounts sufficient to suppress or extinguish a fire. Thehydrofluoroether compounds and the co-extinguishing agent can be in aweight ratio of from about 9:1 to about 1:9.

In some embodiments, the present disclosure is directed to an apparatusfor converting thermal energy into mechanical energy in a Rankine cycle.The apparatus may include a working fluid that includes one or morehydrofluoroether compounds of the present disclosure. The apparatus mayfurther include a heat source to vaporize the working fluid and form avaporized working fluid, a turbine through which the vaporized workingfluid is passed thereby converting thermal energy into mechanicalenergy, a condenser to cool the vaporized working fluid after it ispassed through the turbine, and a pump to recirculate the working fluid.

In some embodiments, the present disclosure relates to a process forconverting thermal energy into mechanical energy in a Rankine cycle. Theprocess may include using a heat source to vaporize a working fluid thatincludes one or more hydrofluoroether compounds of the presentdisclosure to form a vaporized working fluid. In some embodiments, theheat is transferred from the heat source to the working fluid in anevaporator or boiler. The vaporized working fluid may pressurized andcan be used to do work by expansion. The heat source can be of any formsuch as from fossil fuels, e.g., oil, coal, or natural gas.Additionally, in some embodiments, the heat source can come from nuclearpower, solar power, or fuel cells. In other embodiments, the heat can be“waste heat” from other heat transfer systems that would otherwise belost to the atmosphere. The “waste heat,” in some embodiments, can beheat that is recovered from a second Rankine cycle system from thecondenser or other cooling device in the second Rankine cycle.

An additional source of “waste heat” can be found at landfills wheremethane gas is flared off. In order to prevent methane gas from enteringthe environment and thus contributing to global warming, the methane gasgenerated by the landfills can be burned by way of “flares” producingcarbon dioxide and water which are both less harmful to the environmentin terms of global warming potential than methane. Other sources of“waste heat” that can be useful in the provided processes are geothermalsources and heat from other types of engines such as gas turbine enginesthat give off significant heat in their exhaust gases and to coolingliquids such as water and lubricants.

In the provided process, the vaporized working fluid may expanded thougha device that can convert the pressurized working fluid into mechanicalenergy. In some embodiments, the vaporized working fluid is expandedthrough a turbine which can cause a shaft to rotate from the pressure ofthe vaporized working fluid expanding. The turbine can then be used todo mechanical work such as, in some embodiments, operate a generator,thus generating electricity. In other embodiments, the turbine can beused to drive belts, wheels, gears, or other devices that can transfermechanical work or energy for use in attached or linked devices.

After the vaporized working fluid has been converted to mechanicalenergy the vaporized (and now expanded) working fluid can be condensedusing a cooling source to liquefy for reuse. The heat released by thecondenser can be used for other purposes including being recycled intothe same or another Rankine cycle system, thus saving energy. Finally,the condensed working fluid can be pumped by way of a pump back into theboiler or evaporator for reuse in a closed system.

The desired thermodynamic characteristics of organic Rankine cycleworking fluids are well known to those of ordinary skill and arediscussed, for example, in U.S. Pat. Appl. Publ. No. 2010/0139274(Zyhowski et al.). The greater the difference between the temperature ofthe heat source and the temperature of the condensed liquid or aprovided heat sink after condensation, the higher the Rankine cyclethermodynamic efficiency. The thermodynamic efficiency is influenced bymatching the working fluid to the heat source temperature. The closerthe evaporating temperature of the working fluid to the sourcetemperature, the higher the efficiency of the system. Toluene can beused, for example, in the temperature range of 79° C. to about 260° C.,however toluene has toxicological and flammability concerns. Fluids suchas 1,1-dichloro-2,2,2-trifluoroethane and 1,1,1,3,3-pentafluoropropanecan be used in this temperature range as an alternative. But1,1-dichloro-2,2,2-trifluoroethane can form toxic compounds below 300°C. and need to be limited to an evaporating temperature of about 93° C.to about 121° C. Thus, there is a desire for otherenvironmentally-friendly Rankine cycle working fluids with highercritical temperatures so that source temperatures such as gas turbineand internal combustion engine exhaust can be better matched to theworking fluid.

The present disclosure relates to the use of the hydrofluoroethercompounds of the present disclosure as nucleating agents in theproduction of polymeric foams and in particular in the production ofpolyurethane foams and phenolic foams. In this regard, in someembodiments, the present disclosure is directed to a foamablecomposition that includes one or more blowing agents, one or morefoamable polymers or precursor compositions thereof, and one or morenucleating agents that include a hydrofluoroether compound of thepresent disclosure.

In some embodiments, a variety of blowing agents may be used in theprovided foamable compositions including liquid or gaseous blowingagents that are vaporized in order to foam the polymer or gaseousblowing agents that are generated in situ in order to foam the polymer.Illustrative examples of blowing agents include hydrochlorofluorocarbons(HCFCs), hydrofluorocarbons (HFCs), hydrochlorocarbons (HCCs),iodofluorocarbons (IFCs), hydrocarbons, hydrofluoroolefins (HFOs) andhydrofluoroethers (HFEs). The blowing agent for use in the providedfoamable compositions can have a boiling point of from about −45° C. toabout 100° C. at atmospheric pressure. Typically, at atmosphericpressure the blowing agent has a boiling point of at least about 15° C.,more typically between about 20° C. and about 80° C. The blowing agentcan have a boiling point of between about 30° C. and about 65° C.Further illustrative examples of blowing agents that can be used in theinvention include aliphatic and cycloaliphatic hydrocarbons having about5 to about 7 carbon atoms, such as n-pentane and cyclopentane, esterssuch as methyl formate, HFCs such as CF₃CF₂CHFCHFCF₃, CF₃CH₂CF₂H,CF₃CH₂CF₂CH₃, CF₃CF₂H, CH₃CF₂H (HFC-152a), CF₃CH₂CH₂CF₃ and CHF₂CF₂CH₂F,HCFCs such as CH₃CCl₂F, CF₃CHCl₂, and CF₂HCl, HCCs such as2-chloropropane, and IFCs such as CF₃I, and HFEs such as C₄F₉OCH₃ andHFOs such as CF₃CF═CH₂, CF₃CH═CHF and CF₃CH═CHCl. In certainformulations CO₂ generated from the reaction of water with foamprecursor such as an isocyanate can be used as a blowing agent.

In various embodiments, the provided foamable composition may alsoinclude one or more foamable polymers or a precursor compositionthereof. Foamable polymers suitable for use in the provided foamablecompositions include, for example, polyolefins, e.g., polystyrene,poly(vinyl chloride), and polyethylene. Foams can be prepared fromstyrene polymers using conventional extrusion methods. The blowing agentcomposition can be injected into a heat-plastified styrene polymerstream within an extruder and admixed therewith prior to extrusion toform foam. Representative examples of suitable styrene polymers include,for example, the solid homopolymers of styrene, α-methylstyrene,ring-alkylated styrenes, and ring-halogenated styrenes, as well ascopolymers of these monomers with minor amounts of other readilycopolymerizable olefinic monomers, e.g., methyl methacrylate,acrylonitrile, maleic anhydride, citraconic anhydride, itaconicanhydride, acrylic acid, N-vinylcarbazole, butadiene, anddivinylbenzene. Suitable vinyl chloride polymers include, for example,vinyl chloride homopolymer and copolymers of vinyl chloride with othervinyl monomers. Ethylene homopolymers and copolymers of ethylene with,e.g., 2-butene, acrylic acid, propylene, or butadiene may also beuseful. Mixtures of different types of polymers can be employed. Invarious embodiments, the foamable compositions of the present disclosuremay have a molar ratio of nucleating agent to blowing agent of no morethan 1:50, 1:25, 1:9, or 1:7, 1:3, or 1:2.

Other conventional components of foam formulations can, optionally, bepresent in the foamable compositions of the present disclosure. Forexample, cross-linking or chain-extending agents, foam-stabilizingagents or surfactants, catalysts and fire-retardants can be utilized.Other possible components include fillers (e.g., carbon black),colorants, fungicides, bactericides, antioxidants, reinforcing agents,antistatic agents, and other additives or processing aids.

In some embodiments, polymeric foams can be prepared by vaporizing atleast one liquid or gaseous blowing agent or generating at least onegaseous blowing agent in the presence of at least one foamable polymeror a precursor composition thereof and a nucleating agent as describedabove. In further embodiments, polymeric foams can be prepared using theprovided foamable compositions by vaporizing (e.g., by utilizing theheat of precursor reaction) at least one blowing agent in the presenceof a nucleating agent as described above, at least one organicpolyisocyanate and at least one compound containing at least tworeactive hydrogen atoms. In making a polyisocyanate-based foam, thepolyisocyanate, reactive hydrogen-containing compound, and blowing agentcomposition can generally be combined, thoroughly mixed (using, e.g.,any of the various known types of mixing head and spray apparatus), andpermitted to expand and cure into a cellular polymer. It is oftenconvenient, but not necessary, to preblend certain of the components ofthe foamable composition prior to reaction of the polyisocyanate and thereactive hydrogen-containing compound. For example, it is often usefulto first blend the reactive hydrogen-containing compound, blowing agentcomposition, and any other components (e.g., surfactant) except thepolyisocyanate, and to then combine the resulting mixture with thepolyisocyanate. Alternatively, all components of the foamablecomposition can be introduced separately. It is also possible topre-react all or a portion of the reactive hydrogen-containing compoundwith the polyisocyanate to form a prepolymer.

In some embodiments, the present disclosure is directed to dielectricfluids that include one or more hydrofluoroether compounds of thepresent disclosure, as well as to electrical devices (e.g., capacitors,switchgear, transformers, or electric cables or buses) that include suchdielectric fluids. For purposes of the present application, the term“dielectric fluid” is inclusive of both liquid dielectrics and gaseousdielectrics. The physical state of the fluid, gaseous or liquid, isdetermined at the operating conditions of temperature and pressure ofthe electrical device in which it is used.

In some embodiments, the dielectric fluids include one or morehydrofluoroether compounds of the present disclosure and, optionally,one or more second dielectric fluids. Suitable second dielectric fluidsinclude, for example, air, nitrogen, helium, argon, and carbon dioxide,or combinations thereof. The second dielectric fluid may be anon-condensable gas or an inert gas. Generally, the second dielectricfluid may be used in amounts such that vapor pressure is at least 70 kPaat 25° C., or at the operating temperature of the electrical device.

The dielectric fluids of the present application are useful forelectrical insulation and for arc quenching and current interruptionequipment used in the transmission and distribution of electricalenergy. Generally, there are three major types of electrical devices inwhich the fluids of the present disclosure can be used: (1)gas-insulated circuit breakers and current-interruption equipment, (2)gas-insulated transmission lines, and (3) gas-insulated transformers.Such gas-insulated equipment is a major component of power transmissionand distribution systems.

In some embodiments, the present disclosure provides electrical devices,such as capacitors, comprising metal electrodes spaced from each othersuch that the gaseous dielectric fills the space between the electrodes.The interior space of the electrical device may also comprise areservoir of the liquid dielectric fluid which is in equilibrium withthe gaseous dielectric fluid. Thus, the reservoir may replenish anylosses of the dielectric fluid.

In some embodiments, the present disclosure relates to coatingcompositions that include a solvent composition that one or morehydrofluoroether compounds of the present disclosure, and one or morecoating materials which are soluble or dispersible in the solventcomposition.

In various embodiments, the coating materials of the coatingcompositions may include pigments, lubricants, stabilizers, adhesives,anti-oxidants, dyes, polymers, pharmaceuticals, release agents,inorganic oxides, and the like, and combinations thereof. For example,coating materials may include perfluoropolyether, hydrocarbon, andsilicone lubricants; amorphous copolymers of tetrafluoroethylene;polytetrafluoroethylene; or combinations thereof. Further examples ofsuitable coating materials include titanium dioxide, iron oxides,magnesium oxide, perfluoropolyethers, polysiloxanes, stearic acid,acrylic adhesives, polytetrafluoroethylene, amorphous copolymers oftetrafluoroethylene, or combinations thereof.

In some embodiments, the above-described coating compositions can beuseful in coating deposition, where the hydrofluoroether compoundfunction as a carrier for a coating material to enable deposition of thematerial on the surface of a substrate. In this regard, the presentdisclosure further relates to a process for depositing a coating on asubstrate surface using the coating composition. The process comprisesthe step of applying to at least a portion of at least one surface of asubstrate a coating of a liquid coating composition comprising (a) asolvent composition containing one or more hydrofluoroether compounds ofthe present disclosure; and (b) one or more coating materials which aresoluble or dispersible in the solvent composition. The solventcomposition can further comprise one or more co-dispersants orco-solvents and/or one or more additives (e.g., surfactants, coloringagents, stabilizers, anti-oxidants, flame retardants, and the like).Preferably, the process further comprises the step of removing thesolvent composition from the coating by, e.g., allowing evaporation(which can be aided by the application of, e.g., heat or vacuum).

In various embodiments, to form a coating composition, the components ofthe coating composition (i.e., the hydrofluoroether compound(s), thecoating material(s), and any co-dispersant(s) or co-solvent(s) utilized)can be combined by any conventional mixing technique used fordissolving, dispersing, or emulsifying coating materials, e.g., bymechanical agitation, ultrasonic agitation, manual agitation, and thelike. The solvent composition and the coating material(s) can becombined in any ratio depending upon the desired thickness of thecoating. For example, the coating material(s) may constitute from about0.1 to about 10 weight percent of the coating composition.

In illustrative embodiments, the deposition process of the disclosurecan be carried out by applying the coating composition to a substrate byany conventional technique. For example, the composition can be brushedor sprayed (e.g., as an aerosol) onto the substrate, or the substratecan be spin-coated. In some embodiments, the substrate may be coated byimmersion in the composition. Immersion can be carried out at anysuitable temperature and can be maintained for any convenient length oftime. If the substrate is a tubing, such as a catheter, and it isdesired to ensure that the composition coats the lumen wall, thecomposition may be drawn into the lumen by the application of reducedpressure.

In various embodiments, after a coating is applied to a substrate, thesolvent composition can be removed from the coating (e.g., byevaporation). If desired, the rate of evaporation can be accelerated byapplication of reduced pressure or mild heat. The coating can be of anyconvenient thickness, and, in practice, the thickness will be determinedby such factors as the viscosity of the coating material, thetemperature at which the coating is applied, and the rate of withdrawal(if immersion is utilized).

Both organic and inorganic substrates can be coated by the processes ofthe present disclosure. Representative examples of the substratesinclude metals, ceramics, glass, polycarbonate, polystyrene,acrylonitrile-butadiene-styrene copolymer, natural fibers (and fabricsderived therefrom) such as cotton, silk, fur, suede, leather, linen, andwool, synthetic fibers (and fabrics) such as polyester, rayon, acrylics,nylon, or blends thereof, fabrics including a blend of natural andsynthetic fibers, and composites of the foregoing materials. In someembodiments, substrates that may be coated include, for example,magnetic hard disks or electrical connectors with perfluoropolyetherlubricants or medical devices with silicone lubricants.

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more hydrofluoroether compounds of thepresent disclosure, and one or more co-solvents.

In some embodiments, the hydrofluoroether compounds may be present in anamount greater than 50 weight percent, greater than 60 weight percent,greater than 70 weight percent, or greater than 80 weight percent basedupon the total weight of the hydrofluoroether compounds and theco-solvent(s).

In various embodiments, the cleaning composition may further comprise asurfactant. Suitable surfactants include those surfactants that aresufficiently soluble in the fluorinated olefin, and which promote soilremoval by dissolving, dispersing or displacing the soil. One usefulclass of surfactants are those nonionic surfactants that have ahydrophilic-lipophilic balance (HLB) value of less than about 14.Examples include ethoxylated alcohols, ethoxylatedalkyl phenols,ethoxylated fatty acids, alkylarysulfonates, glycerol esters,ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures ofsurfactants having complementary properties may be used in which onesurfactant is added to the cleaning composition to promote oily soilremoval and another added to promote water-soluble oil removal. Thesurfactant, if used, can be added in an amount sufficient to promotesoil removal. Typically, surfactant is added in amounts from about 0.1to 5.0 wt. %, preferably in amounts from about 0.2 to 2.0 wt. % of thecleaning composition.

In illustrative embodiments, the co-solvent may include alcohols,ethers, alkanes, alkenes, haloalkenes, perfluorocarbons, perfluorinatedtertiary amines, perfluoroethers, cycloalkanes, esters, ketones,aromatics, haloaromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, or mixtures thereof.Representative examples of co-solvents which can be used in the cleaningcomposition include methanol, ethanol, isopropanol, t-butyl alcohol,methyl t-butyl ether, methyl t-amyl ether, 1,2-dimethoxyethane,cyclohexane, 2,2,4-trimethylpentane, n-decane, terpenes (e.g., a-pinene,camphene, and limonene), trans-1,2-dichloroethylene,cis-1,2-dichloroethylene, methylcyclopentane, decalin, methyl decanoate,t-butyl acetate, ethyl acetate, diethyl phthalate, 2-butanone, methylisobutyl ketone, naphthalene, toluene, p-chlorobenzotrifluoride,trifluorotoluene, bis(trifluoromethyl)benzenes, hexamethyl disiloxane,octamethyl trisiloxane, perfluorohexane, perfluoroheptane,perfluorooctane, perfluorotributylamine, perfluoro-N-methyl morpholine,perfluoro-2-butyl oxacyclopentane, methylene chloride,chlorocyclohexane, 1-chlorobutane, 1,1-dichloro-1-fluoroethane,1,1,1-trifluoro-2,2-dichloroethane,1,1,1,2,2-pentafluoro-3,3-dichloropropane,1,1,2,2,3-pentafluoro-1,3-dichloropropane, 2,3-dihydroperfluoropentane,1,1,1,2,2,4-hexafluorobutane,1-trifluoromethyl-1,2,2-trifluorocyclobutane,3-methyl-1,1,2,2-tetrafluorocyclobutane, 1-hydropentadecafluoroheptane,or mixtures thereof.

In some embodiments, the present disclosure relates to a process forcleaning a substrate. The cleaning process can be carried out bycontacting a contaminated substrate with a cleaning composition asdiscussed above. The hydrofluoroether compounds can be utilized alone orin admixture with each other or with other commonly-used cleaningsolvents, e.g., alcohols, ethers, alkanes, alkenes, perfluorocarbons,perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters,ketones, aromatics, siloxanes, hydrochlorocarbons,hydrochlorofluorocarbons, hydrofluorocarbons, or mixtures thereof. Suchco-solvents can be chosen to modify or enhance the solvency propertiesof a cleaning composition for a particular use and can be utilized inratios (of co-solvent to hydrofluoroether compounds) such that theresulting composition has no flash point. If desirable for a particularapplication, the cleaning composition can further contain one or moredissolved or dispersed gaseous, liquid, or solid additives (for example,carbon dioxide gas, surfactants, stabilizers, antioxidants, or activatedcarbon).

In some embodiments, the present disclosure relates to cleaningcompositions that include one or more hydrofluoroether compounds of thepresent disclosure and optionally one or more surfactants. Suitablesurfactants include those surfactants that are sufficiently soluble inthe hydrofluoroether compounds, and which promote soil removal bydissolving, dispersing or displacing the soil. One useful class ofsurfactants are those nonionic surfactants that have ahydrophilic-lipophilic balance (HLB) value of less than about 14.Examples include ethoxylated alcohols, ethoxylated alkylphenols,ethoxylated fatty acids, alkylaryl sulfonates, glycerol esters,ethoxylated fluoroalcohols, and fluorinated sulfonamides. Mixtures ofsurfactants having complementary properties may be used in which onesurfactant is added to the cleaning composition to promote oily soilremoval and another added to promote water-soluble soil removal. Thesurfactant, if used, can be added in an amount sufficient to promotesoil removal. Typically, surfactant may be added in amounts from 0.1 to5.0 wt. % or from 0.2 to 2.0 wt. % of the cleaning composition.

The cleaning processes of the disclosure can also be used to dissolve orremove most contaminants from the surface of a substrate. For example,materials such as light hydrocarbon contaminants; higher molecularweight hydrocarbon contaminants such as mineral oils and greases;fluorocarbon contaminants such as perfluoropolyethers,bromotrifluoroethylene oligomers (gyroscope fluids), andchlorotrifluoroethylene oligomers (hydraulic fluids, lubricants);silicone oils and greases; solder fluxes; particulates; water; and othercontaminants encountered in precision, electronic, metal, and medicaldevice cleaning can be removed.

The cleaning compositions can be used in either the gaseous or theliquid state (or both), and any of known or future techniques for“contacting” a substrate can be utilized. For example, a liquid cleaningcomposition can be sprayed or brushed onto the substrate, a gaseouscleaning composition can be blown across the substrate, or the substratecan be immersed in either a gaseous or a liquid composition. Elevatedtemperatures, ultrasonic energy, and/or agitation can be used tofacilitate the cleaning. Various different solvent cleaning techniquesare described by B. N. Ellis in Cleaning and Contamination ofElectronics Components and Assemblies, Electrochemical PublicationsLimited, Ayr, Scotland, pages 182-94 (1986).

Both organic and inorganic substrates can be cleaned by the processes ofthe present disclosure. Representative examples of the substratesinclude metals; ceramics;

glass; polycarbonate; polystyrene; acrylonitrile-butadiene-styrenecopolymer; natural fibers (and fabrics derived therefrom) such ascotton, silk, fur, suede, leather, linen, and wool; synthetic fibers(and fabrics) such as polyester, rayon, acrylics, nylon, or blendsthereof; fabrics comprising a blend of natural and synthetic fibers; andcomposites of the foregoing materials. In some embodiments, the processmay be used in the precision cleaning of electronic components (e.g.,circuit boards), optical or magnetic media, or medical devices.

In some embodiments, the present disclosure further relates toelectrolyte compositions that include one or more hydrofluoroetherolefin compounds of the present disclosure. The electrolyte compositionsmay comprise (a) a solvent composition including one or more of thehydrofluoroether olefin compounds; and (b) at least one electrolytesalt. The electrolyte compositions of the present disclosure exhibitexcellent oxidative stability, and when used in high voltageelectrochemical cells (such as rechargeable lithium ion batteries)provide outstanding cycle life and calendar life. For example, when suchelectrolyte compositions are used in an electrochemical cell with agraphitized carbon electrode, the electrolytes provide stable cycling toa maximum charge voltage of at least 4.5V and up to 6.0V vs. Li/Li⁺.

Electrolyte salts that are suitable for use in preparing the electrolytecompositions of the present diclosure include those salts that compriseat least one cation and at least one weakly coordinating anion (theconjugate acid of the anion having an acidity greater than or equal tothat of a hydrocarbon sulfonic acid (for example, abis(perfluoroalkanesulfonyl)imide anion); that are at least partiallysoluble in a selected hydrofluoroether compound (or in a blend thereofwith one or more other hydrofluoroether compounds or one or moreconventional electrolyte solvents); and that at least partiallydissociate to form a conductive electrolyte composition. The salts maybe stable over a range of operating voltages, are non-corrosive, and arethermally and hydrolytically stable. Suitable cations include alkalimetal, alkaline earth metal, Group IIB metal, Group IIIB metal,transition metal, rare earth metal, and ammonium (for example,tetraalkylammonium or trialkylammonium) cations, as well as a proton. Insome embodiments, cations for battery use include alkali metal andalkaline earth metal cations. Suitable anions includefluorine-containing inorganic anions such as (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻,AsF₆ ⁻, and SbF₆ ⁻; CIO₄ ⁻; HSO₄ ⁻; H₂PO₄ ⁻; organic anions such asalkane, aryl, and alkaryl sulfonates; fluorine-containing andnonfluorinated tetraarylborates; carboranes and halogen-, alkyl-, orhaloalkylsubstituted carborane anions including metallocarborane anions;and fluorine-containing organic anions such asperfluoroalkanesulfonates, cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)imides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides; and the like. Preferred anionsfor battery use include fluorine-containing inorganic anions (forexample, (FSO₂)₂N⁻, BF₄ ⁻, PF₆ ⁻, and AsF₆ ⁻) and fluorine-containingorganic anions (for example, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides). The fluorine-containing organicanions can be either fully fluorinated, that is perfluorinated, orpartially fluorinated (within the organic portion thereof). In someembodiments, the fluorine-containing organic anion is at least about 80percent fluorinated (that is, at least about 80 percent of thecarbon-bonded substituents of the anion are fluorine atoms). In someembodiments, the anion is perfluorinated (that is, fully fluorinated,where all of the carbon-bonded substituents are fluorine atoms). Theanions, including the perfluorinated anions, can contain one or morecatenary heteroatoms such as, for example, nitrogen, oxygen, or sulfur.In some embodiments, fluorine-containing organic anions includeperfluoroalkanesulfonates, bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides.

In some embodiments, the electrolyte salts may include lithium salts.Suitable lithium salts include, for example, lithiumhexafluorophosphate, lithium bis(trifluoromethanesulfonyl)imide, lithiumbis(perfluoroethanesulfonyl)imide, lithium tetrafluoroborate, lithiumperchlorate, lithium hexafluoroarsenate, lithiumtrifluoromethanesulfonate, lithiumtris(trifluoromethanesulfonyl)methide, lithium bis(fluorosulfonyl)imide(Li-FSI), and mixtures of two or more thereof.

The electrolyte compositions of the present disclosure can be preparedby combining at least one electrolyte salt and a solvent compositionincluding at least one hydrofluoroether olefin compound of the presentdisclosure, such that the salt is at least partially dissolved in thesolvent composition at the desired operating temperature. Thehydrofluoroether compounds (or a normally liquid composition including,consisting, or consisting essentially thereof) can be used in suchpreparation.

In some embodiments, the electrolyte salt is employed in the electrolytecomposition at a concentration such that the conductivity of theelectrolyte composition is at or near its maximum value (typically, forexample, at a Li molar concentration of around 0.1-4.0 M, or 1.0-2.0 M,for electrolytes for lithium batteries), although a wide range of otherconcentrations may also be employed.

In some embodiments, one or more conventional electrolyte solvents aremixed with the hydrofluoroether compound(s) (for example, such that thehydrofluoroether(s) constitute from about 1 to about 80 or 90 percent ofthe resulting solvent composition). Useful conventional electrolytesolvents include, for example, organic and fluorine-containingelectrolyte solvents (for example, propylene carbonate, ethylenecarbonate, dimethyl carbonate, diethyl carbonate, ethyl methylcarbonate, dimethoxyethane, 7-butyrolactone, diglyme (that is,diethylene glycol dimethyl ether), tetraglyme (that is, tetraethyleneglycol dimethyl ether), monofluoroethylene carbonate, vinylenecarbonate, ethyl acetate, methyl butyrate, tetrahydrofuran,alkyl-substituted tetrahydrofuran, 1,3-dioxolane, alkyl-substituted1,3-dioxolane, tetrahydropyran, alkyl-substituted tetrahydropyran, andthe like, and mixtures thereof). Other conventional electrolyteadditives (for example, a surfactant) can also be present, if desired.

The present disclosure further relates to electrochemical cells (e.g.,fuel cells, batteries, capacitors, electrochromic windows) that includethe above-described electrolyte compositions. Such an electrochemicalcells may include a positive electrode, a negative electrode, aseparator, and the above-described electrolyte composition.

An electrochemical device using the electrolyte compositions describedherein may, in some embodiments, have a discharge capacity of greaterthan 50%, preferably greater than 80% of theoretical, at a dischargecurrent of up to 12 C. An electrochemical cell including the electrolytecomposition described in this disclosure may, in some embodiments, havea charge capacity of greater than about 40%, preferably greater thanabout 60% of theoretical, at a charge current of up to 6 C. Anelectrochemical cell including the electrolyte compositions describedherein may, in some embodiments, have excellent low temperatureperformance, and may retain over 90% of its discharge capacity at 25° C.when exposed to ambient temperatures from 0° C. to −20° C. Theelectrochemical cell including the presently described electrolytecompositions may, in some embodiments, retain a discharge capacity ofgreater than 150 mAh per gram of cathode over up to 30 charging cyclesat up to 4.5V.

A variety of negative and positive electrodes may be employed in theelectrochemical cells. Representative negative electrodes includegraphitic carbons e. g., those having a spacing between (002)crystallographic planes, d₀₀₂, of 3.45 A>d₀₀₂>3.354 A and existing informs such as powders, flakes, fibers or spheres (e. g., mesocarbonmicrobeads); Li_(4/3)Ti_(5/3)0₄ the lithium alloy compositions describedin U.S. Pat. No. 6,203,944 (Turner '944) entitled “ELECTRODE FOR ALITHIUM BATTERY” and PCT Published Patent Application No. WO 00103444(Turner PCT) entitled “ELECTRODE MATERIAL AND COMPOSITIONS”; andcombinations thereof. Representative positive electrodes includeLiFePO₄, LiMnPO₄, LiCoPO₄, LiMn₂O₄, LiCoO₂ and combinations thereof. Thenegative or positive electrode may contain additives such as will befamiliar to those skilled in the art, e. g., carbon black for negativeelectrodes and carbon black, flake graphite and the like for positiveelectrodes.

The electrochemical devices of the invention can be used in variouselectronic articles such as computers, power tools, automobiles,telecommunication devices, and the like.

EMBODIMENTS

1. A hydrofluoroether compound represented by the following generalformula (I):

wherein,

-   -   (i) Rf₃ is F, Rf₄ is CF₃, and Rf₁ and Rf₂ are independently        perfluoroalkyl groups (a) having 1 to 2 carbon atoms and        optionally comprising at least one catenated heteroatom, or (b)        that are bonded together to form a ring structure having 4-8        carbon atoms and optionally comprising one or more catenated        heteroatoms selected from oxygen, nitrogen or sulfur; or    -   (ii) Rf₃ is CF₃, Rf₄ is F, and Rf₁ and Rf₂ are independently        perfluoroalkyl groups (a) having 1 to 8 carbon atoms and        optionally comprising at least one catenated heteroatom, or (b)        that are bonded together to form a ring structure having 4 to 8        carbon atoms and optionally comprising one or more catenated        heteroatoms selected from oxygen, nitrogen or sulfur; and        wherein

Rfh is a linear, branched, or cyclic alkyl or fluoroalkyl group of from1 to 10 carbon atoms that may be saturated or unsaturated and optionallycontains one or more catenated heteroatoms.

2. A hydrofluoroether compound represented by the following generalformula (II):

wherein,

Rf₅ and Rf₆ are independently perfluoroalkyl groups (i) having 1-8carbon atoms and optionally comprising at least one catenatedheteroatom, or (ii) that are bonded together to form a ring structurehaving 4-8 carbon atoms and optionally comprising one or more catenatedheteroatoms selected from oxygen, nitrogen or sulfur. Each of Rf₇, Rf₈,Rf′₇, and Rf′₈ is independently a F or CF₃ group, with the proviso thatwhen:

Rf₇ is F, Rf₈ is CF_(3,)

Rf₈ is F, Rf₇ is CF₃,

Rf′₇is F, Rf′₈ is CF₃,

Rf′₈ is F, Rf′₇ is CF₃, and

Rfh₁ is a linear, branched, cyclic, or acyclic alkylene orfluoroalkylene group having from 1 to 8 carbon atoms and optionallycomprising one or more catenated heteroatoms.

3. A fire extinguishing composition comprising:

(a) a hydrofluoroether compound according to any one of embodiments 1-2;

(b) at least one co-extinguishing agent comprising one or morehydrofluorocarbons, hydrochlorofluorocarbons, perfluorocarbons,perfluoropolyethers, hydrofluoroethers, hydrofluoropolyethers,chlorofluorocarbons, bromofluorocarbons, bromochlorofluorocarbons,iodofluorocarbons, hydrobromofluorocarbons, fluorinated ketones,hydrobromocarbons, fluorinated olefins, hydrofluoroolefins, fluorinatedsulfones, fluorinated vinylethers, and mixtures thereof,

wherein (a) and (b) are present in an amount sufficient to suppress orextinguish a fire.

4. A fire extinguishing composition according to embodiment 3, wherein(a) and (b) are in a weight ratio of from about 9:1 to about 1:9.5. A method of extinguishing a fire comprising:

applying to the fire a fire extinguishing composition comprising ahydrofluoroether compound according to any one of embodiments 1-2; and

suppressing the fire.

6. A method of extinguishing a fire according to embodiment 5, whereinthe fire extinguishing composition further comprises at least oneco-extinguishing agent comprising one or more hydrofluorocarbons,hydrochlorofluorocarbons, perfluorocarbons, perfluoropolyethers,hydrofluoroethers, hydrofluoropolyethers, chlorofluorocarbons,bromofluorocarbons, bromochlorofluorocarbons, iodofluorocarbons,hydrobromofluorocarbons, fluorinated ketones, hydrobromocarbons,fluorinated olefins, hydrofluoroolefins, fluorinated sulfones,fluorinated vinylethers, and mixtures thereof.7. An apparatus for converting thermal energy into mechanical energy ina Rankine cycle comprising:

a working fluid;

a heat source to vaporize the working fluid and form a vaporized workingfluid;

a turbine through which the vaporized working fluid is passed therebyconverting thermal energy into mechanical energy;

a condenser to cool the vaporized working fluid after it is passedthrough the turbine; and

a pump to recirculate the working fluid,

wherein the working fluid comprises a hydrofluoroether compoundaccording to any one of embodiments 1-2.

8. A process for converting thermal energy into mechanical energy in aRankine cycle comprising:

vaporizing a working fluid with a heat source to form a vaporizedworking fluid;

expanding the vaporized working fluid through a turbine;

cooling the vaporized working fluid using a cooling source to form acondensed working fluid; and

pumping the condensed working fluid;

wherein the working fluid comprises a hydrofluoroether compoundaccording to any one of embodiments 1-2.

9. A process for recovering waste heat comprising:

passing a liquid working fluid through a heat exchanger in communicationwith a process that produces waste heat to produce a vaporized workingfluid;

removing the vaporized working fluid from the heat exchanger;

passing the vaporized working fluid through an expander, wherein thewaste heat is converted into mechanical energy; and

cooling the vaporized working fluid after it has been passed through theexpander;

wherein the working fluid comprises a hydrofluoroether compoundaccording to any one of embodiments 1-2.

10. A foamable composition comprising:

a blowing agent;

a foamable polymer or a precursor composition thereof; and

a nucleating agent, wherein said nucleating agent comprises ahydrofluoroether compound according to any one of embodiments 1-2.

11. A foamable composition according to embodiment 10, wherein thenucleating agent and the blowing agent are in a molar ratio of less than1:2.12. A foamable composition according to any one of embodiments 10-11,wherein the blowing agent comprises an aliphatic hydrocarbon having fromabout 5 to about 7 carbon atoms, a cycloaliphatic hydrocarbon havingfrom about 5 to about 7 carbon atoms, a hydrocarbon ester, water, orcombinations thereof.13. A process for preparing polymeric foam comprising:

vaporizing at least one liquid or gaseous blowing agent or generating atleast one gaseous blowing agent in the presence of at least one foamablepolymer or a precursor composition thereof and a nucleating agent,wherein said nucleating agent comprises a hydrofluoroether compoundingaccording to any one of embodiments 1-2.

14. A foam made with the foamable composition according to embodiment12.15. A device comprising:

a dielectric fluid comprising a hydrofluoroether compound according toany one of embodiments 1-2;

wherein the device is an electrical device.

16. The device of embodiment 15, wherein said electrical devicecomprises a gas-insulated circuit breakers, current-interruptionequipment, a gas-insulated transmission line, a gas-insulatedtransformers, or a gas-insulated substation.17. The device according to any one of embodiments 15-16, wherein thedielectric fluid further comprises a second dielectric gas.18. The device of embodiment 17, wherein the second dielectric gascomprises an inert gas.19. The device of embodiment 18, wherein the second dielectric gascomprises nitrogen, helium, argon, or carbon dioxide.20. A coating composition comprising:

a solvent composition comprising a hydrofluoroether compound accordingto any one of embodiments 1-2; and

a coating material that is soluble or dispersible in said solventcomposition.

21. The coating composition according to embodiment 20, wherein saidcoating material comprises a pigment, lubricant, stabilizer, adhesive,anti-oxidant, dye, polymer, pharmaceutical, release agent, inorganicoxide.22. The composition according to embodiment 20, wherein said coatingmaterial comprises a perfluoropolyether, a hydrocarbon, a siliconelubricant, a copolymer of tetrafluoroethylene, or apolytetrafluoroethylene.23. A cleaning composition comprising:

a hydrofluoroether compound according to any one of embodiments 1-2; anda co-solvent.

24. The composition of embodiment 24, wherein said hydrofluoroethercompound is greater than 50 percent by weight of said composition basedon the total weights of the fluorinated olefin compound and theco-solvent.25. The composition according to any one of embodiments 23-24, whereinsaid co-solvent comprises alcohols, ethers, alkanes, alkenes,haloalkenes, perfluorocarbons, perfluorinated tertiary amines,perfluoroethers, cycloalkanes, esters, ketones, aromatics,haloaromatics, siloxanes, hydrochlorocarbons, hydrochlorofluorocarbons,hydrofluorocarbons, or mixtures thereof.26. A cleaning composition comprising:

a hydrofluoroether compound according to any one of embodiments 1-2; and

a surfactant.

27. The composition of embodiment 26, wherein the cleaning compositioncomprises from 0. 1 to 5 percent by weight surfactant.28. The composition according to any one of embodiments 26-27, whereinthe surfactant comprises a nonionic surfactant comprising an ethoxylatedalcohol, an ethoxylated alkylphenol, an ethoxylated fatty acid, analkylaryl sulfonate, a glycerolester, an ethoxylated fluoroalcohol, afluorinated sulfonamide, or mixtures thereof.29. A process for removing contaminants from a substrate, the processcomprising the steps of:

contacting a substrate with a composition comprising:

-   -   a hydrofluoroether compound according to any one of embodiments        1-2; and    -   a co-solvent.        30. An electrolyte composition comprising:

a solvent composition comprising at least one hydrofluoroether compoundaccording to any one of embodiments 1-2; and

an electrolyte salt.

The operation of the present disclosure will be further described withregard to the following detailed examples. These examples are offered tofurther illustrate various embodiments and techniques. It should beunderstood, however, that many variations and modifications may be madewhile remaining within the scope of the present disclosure.

EXAMPLES Example 1 Preparation of2,2,3,3,5,5,6,6-octafluoro-4-(1,3,3,3-tetrafluoro-2-methoxy-prop-1-enyl)morpholine

2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholinewas prepared using a hot tube reactor. To the hot tube reactor(metallurgy), anhydrous potassium carbonate (400 g, 2.9 mol,Sigma-Aldrich) was charged. The reactor was sealed and connected to ahigh pressure syringe pump. The reactor was heated to a temperature of220° C.2-[difluoro-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)methyl]-2,3,3,3-tetrafluoro-propanoylfluoride (470 g 1.1 mol) (prepared via electrochemical fluorination ofmethyl 2-methyl-3-morpholino-propanoate via a Simons ECF cell ofessentially the type described in U.S. Pat. No. 2,713,593 (Brice et al.)and in R. E. Banks, Preparation, Properties and Industrial Applicationsof Organofluorine Compounds, pages 19-43, Halsted Press, New York(1982)) was then pumped to the hot tube reactor at a rate of 35 mL/hour.The product was collected using a dry ice trap at −78° C. A total of 345g of material was collected which was ˜70% converted to the desiredproduct. The remaining material was unreacted acid fluoride and inertfluorocarbon. The material was fractionally distilled and its boilingpoint is about 85° C. The product structure was verified by GC/MS andF-19 and H-1 NMR.

In a 500 mL round bottom flask equipped with magnetic stirring,condenser controlled with a chiller at 1 deg. C, addition funnel and dryN2 bubbler,2,2,3,3,5,5,6,6-octafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)morpholine(220 g, 0.61 mol), potassium hydroxide (39.9 g, 0.713 mol,Sigma-Aldrich) and Aliquat 336 (1 g, 0.002 mol, Alfa-Aesar) werecharged. The mix was stirred at room temp and methanol (19.5 g, 0.61mol, Alfa-Aesar) was added slowly dropwise via an addition funnel overan hour. Once the methanol charge was added the reaction mixture washeated to 65° C. for 16 hours. After stirring overnight the heat wasremoved and after cooling to room temperature, 100 mL of water wasadded. The mix was stirred and then transferred to a 500 mL separatoryfunnel. The lower FC phase was separated and dried with anhydrousmagnesium sulfate. A total of 138 g of material was collected. Based onGC-FID analysis, the conversion to the desired product was about 75%.This material was fractionally distilled using a concentric tube column.The boiling point of the product is approximately 128° C. The productstructure was confirmed to be a mixture of cis and trans isomers byGC/MS and F-19 and H-1 NMR.

Example 2 Preparation of2,2,3,3,5,5,6,6-octafluoro-4-[2-fluoro-2-methoxy-1-(trifluoromethyl)vinyl]morpholine

4-[2,2-difluoro-1-(trifluoromethyl)vinyl]-2,2,3,3,5,5,6,6-octafluoro-morpholinewas prepared by converting2,2,3,4,4,4-hexafluoro-3-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)butanoylfluoride (prepared via electrochemical fluorination of methyl3-morpholinobutanoate via a Simons ECF cell of essentially the typedescribed in U.S. Pat. No. 2,713,593 (Brice et al.) and in R. E. Banks,Preparation, Properties and Industrial Applications of OrganofluorineCompounds, pages 19-43, Halsted Press, New York (1982)) to the potassiumsalt via titration of methyl2,2,3,4,4,4-hexafluoro-3-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)butanoatewith potassium hydroxide. Potassium2,2,3,4,4,4-hexafluoro-3-(2,2,3,3,5,5,6,6-octafluoromorpholin-4-yl)butanoate(134 g, 0.29 mol) and 200 mL of HT-270 (Solvay-Solexis) were charged toa 500 mL 3-neck round bottom flask. The flask was equipped with overheadstirring, thermocouple, heating mantle and a one-plate simpledistillation column. The mixture was gradually heated up to 210° C. Atotal of 86 g of4-[2,2-difluoro-1-(trifluoromethyl)vinyl]-2,2,3,3,5,5,6,6-octafluoro-morpholinewas collected of which about 70% was the desired product with theremainder being inert fluorocarbon. The reaction was repeated on anotherportion of potassium salt and in total 196 g of the desired olefinintermediate were obtained.

In a 3-neck 250 mL round bottom flask powdered potassium hydroxide(14.16 g, 0.253 mol Sigma-Aldrich),4-[2,2-difluoro-1-(trifluoromethyl)vinyl]-2,2,3,3,5,5,6,6-octafluoro-morpholine(110 g 0.216 mol) and Aliquat 336 (1 g, 0.0024 mol) were charged. Theflask was equipped with overhead stirring, a cold water condenser,thermocouple and heating mantle. Methanol (6.93 g, 0.216 molSigma-Aldrich) was added via an addition funnel and the reaction mixturewas kept cool during the addition with a cold water bath. Once themethanol addition was complete, the reaction was heated to 65 deg. C for24 hours. Water was then added to the mix to dissolve the salts. Themixture was then transferred to a separatory funnel where thefluorochemical phase was separated from the aqueous phase. 89 g of crudeproduct was collected after phase splitting. The fluorochemical wasdried over anhydrous MgSO₄ and then fractionally distilled using aconcentric tube distillation column. A sample of the main distillate cut(B.P.=125° C.) was analyzed by GC/MS, confirming the presence of thedesired product.

Example 3 Preparation of2,2,3,3,5,5,6,6-octafluoro-4-[1,3,3,3-tetrafluoro-2-(2,2,3,3-tetrafluoropropoxy)prop-1-enyl]morpholine

2,2,3,3,5,5,6,6-octafluoro-4-[(E&Z)-1,2,3,3,3-pentafluoroprop-1-enyl]morpholine(200.00 g, >95%), acetonitrile (312 g, Aldrich Anhydrous, 99.8%) andpotassium carbonate (84.214 g, powdered, 325 mesh, Armand Product Co.)were combined in a 3-neck 1000 mL round bottom flask equipped withmagnetic stirring, a water cooled condenser with N₂ inlet, a Claisenadapter with Teflon coated thermocouple probe and addition funnel, Whilereaction mixture was stirring 2,2,3,3-tetrafluoropropanol (76.809 g, TCIAmerica, >98%) was charged to the reaction mixture over 90 minutes. Aslightly exothermic reaction was observed causing the reactiontemperature to rise from 21.3° to 24.4° C. The reaction was allowed toproceed for 18 hours at which time stirring was halted and a sample ofthe bottom layer was removed by pipette and filtered through a 0.2 μmPVDF filter disc. This filtered sample was analyzed by GC-FID showingthe starting propenylamine is 69.8% converted. An additional 20.83 gpotassium carbonate was charged to the reaction mixture in severalportions with stirring at room temperature resulting in a final overallmeasured conversion (by GC) of 95%. The product mixture contained 79% ofthe desired Hydrofluoroether-Olefin (HFE-Olefin) product and 5% of thecorresponding HFE-Hydride, O(CF₂CF₂)₂NCFHCF(CF₃)OCH₂CF₂CF₂H. The crudereaction mix was filtered through a C porosity fritted glass filterfunnel to remove solids. The filtrate was fractionally distilled toremove a majority of the residual starting propenylamine, CH₃CN andunreacted HOCH₂CF₂CF₂H. The fractional distillation was allowed toproceed until the head temp reached 156° C. The crude product remainingin the distillation pot was straw colored and contained some insolubledark sludgy solids. This mixture was filtered through a 1 μm glassfilter disc to remove solids, giving a colored filtrate. The filteredcrude product was transferred to a 250 mL poly bottle, diluted with 142g acetonitrile and treated with 6.36 g KOH powder in two portions toconvert all residual HFE-Hydride byproduct to the desired HFE-Olefinproduct (by dehydrofluorination). After stirring with KOH at roomtemperature for at least a few hours, the treated mixture was filteredby suction through a C porosity fitted glass filter. The desired productwas then isolated from the filtrate and purified by fractionaldistillation through a concentric tube distillation column giving 45.63g of product distillate (B.P.=161-162° C.) as a clear colorless liquidwith an average purity of 97.84% by GC. The product structure,consisting of a mixture of E and Z isomers, was verified by GC/MS and¹⁹F and ¹H NMR spectroscopy.

Example 4 Preparation of1,3,3,3-tetrafluoro-2-methoxy-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-1-en-1-amine

Potassium carbonate (325 mesh) (0.456 g, 3.30 mmol),1,2,3,3,3-pentafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-1-en-1-amine(1 g, 3.00 mmol), and acetonitrile (anhydrous) (2.358 g, 3 mL) wereadded to an 8 mL screw cap vial equipped with a Teflon coated magneticstir bar. Methanol was then added and the biphasic reaction mixture isallowed to stir at room temperature for 96 h. The propenylamine startingmaterial was 44% converted (by GC) under these conditions. The reactionmixture was filtered through a 0.2 μm PVDF filter disc and then dilutedwith water to cause the fluorochemical product mixture to phase separateand to remove residual base and acetonitrile in the upper water phase.The lower fluorochemical phase was analyzed by GC-MS, which verifiedthat the desired HFE-Olefin product, consisting of a mixture of E and Zisomers, was present at 91.3% of the overall mixture. No HFE-Hydridebyproduct was detected.

The following examples (5-11) use the general procedure (A) outlinedhere: Potassium hydroxide (fine powder), alcohol, and acetonitrile areadded to an 8 mL screw cap vial equipped with a Teflon coated magneticstir bar.(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholineis then added and the biphasic reaction mixture is allowed to stir atr.t. for 16 h. The resulting mixture is then diluted with water and thefluorochemical phase is analyzed using GC, GC/MS and NMR.

Example 5 Preparation ofE/Z)-N,N-dimethyl-2-((1,3,3,3-tetrafluoro-1-(perfluoromorpholino)prop-1-en-2-yl)oxy)ethan-1-amine

Following General Procedure A,(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine(1 equiv., 4.71 mmol, 1 mL), KOH (1.2 equiv, 5.65 mmol, 316.99 mg),2-(dimethylamino)ethan-1-ol (1.2 equiv., 5.65 mmol, 518.56 μL) andacetonitrile (1 mL) were added. Analysis by GC and GC/MS indicates 88%yield of the desired product as a mixture of E/Z isomers

Example 6 Preparation of(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(1,3,3,3-tetrafluoro-2-(2-methoxyethoxy)prop-1-en-1-yl)morpholine

Following General Procedure A,(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine(1 equiv., 4.71 mmol, 1 mL), KOH (1.2 equiv, 5.65 mmol, 316.99 mg),2-methoxyethan-1-ol (1.2 equiv., 5.65 mmol, 445.53 μL) and acetonitrile(1 mL) were added. Analysis by GC and GC/MS indicates 78% yield of thedesired product as a mixture of E/Z isomers.

Example 7 Preparation of (E/Z)-4-(2-(cyclop entyloxy)-1,3,3,3-tetrafluoroprop-1-en-1-yl)-2,2,3,3,5,5,6,6-octafluoromorpholine

Following General Procedure A,(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine(1 equiv., 4.71 mmol, 1 mL), KOH (1.2 equiv, 5.65 mmol, 316.99 mg),cyclopentanol (1.2 equiv., 5.65 mmol, 512.81 μL) and acetonitrile (1 mL)were added. Analysis by GC and GC/MS indicates 51% yield of the desiredproduct as a mixture of E/Z isomers.

Example 8 Preparation of(E/Z)-4-(2-(cyclopropylmethoxy)-1,3,3,3-tetrafluoroprop-1-en-1-yl)-2,2,3,3,5,5,6,6-octafluoromorpholine

Following General Procedure A,(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine(1 equiv., 4.71 mmol, 1 mL), KOH (1.2 equiv, 5.65 mmol, 316.99 mg),cyclopropylmethanol (1.2 equiv., 5.65 mmol, 457.76 μL) and acetonitrile(1 mL) were added. Analysis by GC and GC/MS indicates 88% yield of thedesired product as a mixture of E/Z isomers.

Example 9 Preparation of2,2,3,3,5,5,6,6-octafluoro-4-((E/Z)-1,3,3,3-tetrafluoro-2-(((E)-4,4,4-trifluorobut-2-en-1-yl)oxy)prop-1-en-1-yl)morpholine

Following General Procedure A,(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine(1 equiv., 4.71 mmol, 1 mL), KOH (1.2 equiv, 5.65 mmol, 316.99 mg),(E)-4,4,4-trifluorobut-2-en-1-ol (1.2 equiv., 5.65 mmol, 567.15 μL) andacetonitrile (1 mL) were added. Analysis by GC and GC/MS indicates 76%yield of the desired product as a mixture of E/Z isomers.

Example 10 Preparation of(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(1,3,3,3-tetrafluoro-2-((3-methylbut-2-en-1-yl)oxy)prop-1-en-1-yl)morpholine

Following General Procedure A,(E)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine (1equiv., 4.71 mmol, 1 mL), KOH (1.2 equiv, 5.65 mmol, 316.99 mg),3-methylbut-2-en-1-ol (1.2 equiv., 5.65 mmol, 565.88 μL) andacetonitrile (1 mL) were added. Analysis by GC and GC/MS indicates 85%yield of the desired product as a mixture of E/Z isomers.

Example 11 Preparation of 1-(((E/Z)-1,3,3,3-tetrafluoro-1-(perfluoromorpholino)prop-1-en-2-yl)oxy)-4-(((E/Z)-1,3,3,3-tetrafluoro-1-(perfluoromorpholino)prop-1-en-2-yl)oxy)butane:

Following General Procedure A,(E/Z)-2,2,3,3,5,5,6,6-octafluoro-4-(perfluoroprop-1-en-1-yl)morpholine(1 equiv., 4.71 mmol, 1 mL), KOH (1.2 equiv, 5.65 mmol, 316.99 mg),1,4-butandiol (0.5 equiv., 2.35 mmol, 208.62 μL) and acetonitrile (1 mL)were added. Analysis by GC and GC/MS indicates 56% yield of the desiredproduct as a mixture of E/Z isomers.

Examples 12-19

The following examples were prepared by the following general method:

K₂CO₃ powder, anhydrous CH₃CN, PF-propenylamine and the alcohol reagentwere charged to a 7 mL glass vial in the order indicated (in air). Amini stir bar was added and the vial was then tightly capped and rapidstirring initiated at the temperature indicated in the Table. Thereaction was allowed to proceed with stirring for a minimum of 16 hours,while monitoring the progress of the reaction periodically by GC-FID byremoving small aliquots of the reaction mixture and injecting neat. Oncethe reaction was judged to be nearly complete, the reaction solution wasfiltered by syringe to remove suspended solids and the filtrate wassubmitted for GC-MS analysis to confirm tentative GC-FID peakassignments and identify the major products formed. This information wasthen used to calculate the yield of the desired alcohol additionproducts and the olefin/hydride ratio.

CH3CN Rxn GC Area % Olefin/ K2CO3 Solvent Time Reaction Yield of HydrideEx PF-Propenylamine mMoles Alcohol mMoles (mMoles) (mLs) (Hrs) Temp °C.Desired * Ratio ** 12

2.770 CF3CH2OH 2.909 4.494 3 96 21 89.6 11.1 13

2.770 HCF2CF2CH2OH 2.909 3.843 3 48 21 84.3 17.3 14

2.770 CF3CFHCF2CH2OH 2.909 2.909 3 96 22 87.2 22.7 15

2.770 C2F5CH2OH 2.909 2.909 3 96 22 79.9 34.6 16

2.770 (CF3)2CHOH 2.909 2.909 3 72 22 75.1 3.9 17

2.770 CF3CFHCF2CH(CH3)OH 2.909 2.909 3 96 22 90.0 59.5 18

3.003 HCF2CF2CH2OH 3.299 3.299 3 96 22 95.9 66.7 19

3.003 CF3CFHCF2CH2OH 3.299 3.299 3 96 22 91.2 33.3 * Based on conversionof PF-Propenylamine (limiting reagent) to desired HFE-Olefin (major) andHFE-Hydride (minor byproduct) addition products by GC-FID. ByproductHFE-Hydride is readily converted back to desired HFE-Olefin by treatmentwith strong base (e.g., KOH, etc). ** HFE-Olefin/HFE-Hydride ratio byrelative GC-FID peak area

Using the procedure and reagents described in Examples 12-19, thefollowing hydrofluoroether (or HFE-Olefin) compounds (a mixture of E andZ isomers) were successfully prepared in high yield and characterized byGC-MS:

Ex Product 12

13

14

15

16

17

18

19

Example 20 Preparation of1,3,3,3-tetrafluoro-2-(2,2,3,3-tetrafluoropropoxy)-N,N-bis(trifluoromethyl)prop-1-en-1-amine

(E&Z)-1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-ene-1-amine(200.00 g, 99.9%), acetone (395.5 g, EMD HPLC Grade) and potassiumcarbonate (107.42 g, powdered, 325mesh, Armand Product Co.) werecombined in a 3-neck, 1000 mL round bottom flask equipped with magneticstirring, a chiller cooled condenser set to 0° C. with N₂ inlet, aClaisen adapter with Teflon coated thermocouple probe and additionfunnel. The starting reaction mixture initially contained two liquidphases. While reaction mixture was stirring at room temperature,2,2,3,3-tetrafluoropropanol (97.98 g, TCI America, >98%) was added overa 90 minute period. A slightly exothermic reaction was observed causingthe reaction temperature to rise from 21.3° to 24.4° C. The reactionmixture appeared to be a single liquid phase once alcohol addition wascomplete. The reaction was allowed to proceed at room temperature for 48hours after which time stirring was halted and a sample of the reactionwas removed by pipette and filtered through a 0.2 μm PVDF filter disc.This filtered sample was analyzed by GC-FID showing the startingpropenyl amine was 82% converted. An additional 19.88 g potassiumcarbonate was charged to the mixture and the reaction was allowed toproceed for an additional 3 days at room temperature with stirring.Analysis by GC-FID, as described above, indicated that the reaction was91% complete (i.e., 9% of the starting material remained). An additional20.14 g potassium carbonate was charged to the reaction mixture andallowed to stir for another 24 hours. Then stirring was halted and thebottom layer of the reaction mixture was evaluated by GC-FID. The amountof propenyl amine starting material converted was >95%. The crudereaction mixture was filtered through 20-25 μm filter paper to removesolids. The filtrate collected was transferred to a reparatory funneland washed with 500 mL water causing the dense fluorochemical productphase to separate from the upper aqueous phase. The fluorochemical phasewas isolated and washed twice with additional water. GC analysisindicated that the crude fluorochemical product was 99.70% desiredproduct mixture, consisting of 96.59% desired HFE-Olefin and 3.11%HFE-Hydride byproduct. The residual HFE-Hydride byproduct was convertedto the desired HFE-Olefin product (by dehydrofluorination) by treatmentof the crude product at room temperature with 8.69 g potassium hydroxide(powdered, Fluka, >85%.) charged in three portions along with 3.25 gacetonitrile (Aldrich Anhydrous, 99.8). Three 100 mL water washes wereused to remove residual potassium hydroxide and acetonitrile from thetreated product. The fluorochemical product phase was then dried over 3A molecular sieves for 5 days, and purified by fractional distillationthrough a concentric tube distillation column giving 110.64 g of productdistillate (B.P.=120-124° C.) as a clear colorless liquid with anaverage purity of 99.63% by GC. The product structure, consisting of amixture of E and Z isomers, was verified by GC/MS and ¹⁹F and ¹H NMRspectroscopy.

Example 21 Preparation of4-[2-ethoxy-1,3,3,3-tetrafluoro-prop-1-enyl]-2,2,3,3,5,5,6,6-octafluoro-morpholine

2,2,3,3,5,5,6,6-octafluoro-4-[(E&Z)-1,2,3,3,3-pentafluoroprop-1-enyl]morpholine(200.00 g, >95%), acetonitrile (312 g, Aldrich Anhydrous, 99.8%) andpotassium hydroxide (32.63 g, powdered, Fluka, >85%.) were combined in a3-neck 1000 mL round bottom flask equipped with magnetic stirring, awater cooled condenser with N₂ inlet, a Claisen adapter with Tefloncoated thermocouple probe and addition funnel, While reaction mixturewas stirring at room temperature, ethanol (26.80 g, undenatured, 200proof) was charged to the reaction mixture over a 75 minute period. Aslightly exothermic reaction was observed causing the reactiontemperature to rise from 22.2° to 24.6°. The reaction was allowed toproceed for 24 hours after which time stirring was halted and a sampleof the bottom layer was removed by pipette and filtered through a 0.2 μmPVDF filter disc. This filtered sample was analyzed by GC-FID indicatingthat the starting propenyl amine was 82% converted. An additional 9.46 gpotassium hydroxide was charged to the reaction mixture in severalportions with stirring at room temperature. The reaction was allowed toproceed overnight at room temperature. Then, stirring was halted and thebottom layer of the reaction mixture was evaluated as above by GC-FID,indicating that >98% of the starting material was converted. Thefluorochemical product mixture contained 96% desired product(HFE-Olefin) and 1% HFE-Hydride byproduct, O(CF₂CF₂)₂NCFHCF(CF₃)OCH₂CH₃,by GC. The crude reaction mix was filtered through 20-25 μm filter paperto remove insoluble solids. The filtrate was combined with 100 mL ofwater causing the dense fluorochemical product to phase separate fromthe upper aqueous layer. The crude fluorochemical product phase wasisolated, dried over 3 A molecular sieves, and purified by fractionaldistillation using a concentric tube distillation column. Fractionaldistillation proved incapable of removing all the residual CH₃CN solventand HFE-Hydride byproduct, so the collected product distillate fractionswere recombined, treated with 2 portions of KOH (powder) (4.80 g total)and stirred overnight at room temperature to convert all residualHFE-Hydride byproduct to the desired HFE-Olefin product (bydehydrofluorination). The treated product mixture was then filteredthrough 20-25 μm filter paper to remove the insoluble KOH solids andwashed with three 50 mL portions of DI water to remove the residualacetonitrile. The washed fluorochemical phase was transferred to anErlenmeyer flask, dried over 3 A molecular sieves for three days, andthen purified by fractional distillation through a concentric tubedistillation column. A total of 71.69 g of product distillate wascollected as a clear colorless liquid (B.P.=136-141° C.) with an averagepurity of 99.64% by GC. The product structure, consisting of a mixtureof E and Z isomers, was verified by GC/MS and ¹⁹F and ¹H NMRspectroscopy.

Example 22 Preparation of2,3,3,5,5,6-hexafluoro-4-(1,3,3,3-tetrafluoro-2-methoxy-prop-1-enyl)-2,6-bis(trifluoromethyl)morpholine

In a 100 mL 2-neck round bottom flask equipped with magnetic stirring,cold water condenser, dry N2 bubbler and a thermocouple,2,3,3,5,5,6-hexafluoro-4-(1,2,3,3,3-pentafluoroprop-1-enyl)-2,6-bis(trifluoromethyl)morpholine(13 g, 28.2 mmol), powdered potassium hydroxide (1.9 g, 29 mmol),acetonitrile (50 mL), methanol (1.1 g, 34 mmol) and Adogen 464 (0.42 g,1.0 mmol) were combined and stirred for 16 hours at 50 deg. C. A sampleof the fluorochemical phase was then analyzed by GC-FID and GC/MS whichshowed 49.2% of the desired product structure.

The following examples (23-24) use the general procedure (B) outlinedhere: Potassium hydroxide (fine powder), alcohol, and acetonitrile wereadded to an 7 mL screw cap vial equipped with a Teflon coated magneticstir bar.(E/Z)-1,2,3,3,3-pentafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-1-en-1-aminewas then added and the biphasic reaction mixture was allowed to stir atr.t. for 17 h. The resulting mixture was then filtered via syringethrough a 0.45 micron Teflon membrane to remove solids and analyzed byGC-FID and GC/MS.

Example 23 Preparation of(E/Z)-2-ethoxy-1,3,3,3-tetrafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-1-en-1-amine

Following General Procedure B,(E/Z)-1,2,3,3,3-pentafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-1-en-1-amine(1 equiv., 3.00 mmol, 1.0 g), KOH (1.6 equiv, 4.80 mmol, 270 mg), andethanol (1.2 equiv., 3.60 mmol, 210 μL) were reacted in acetonitrile (3mL). Analysis of the acetonitrile solution by GC and GC/MS indicates94.4% yield of the desired HFE-Olefin product was obtained as a mixtureof E/Z isomers, based on limiting reagent.

Example 24 Preparation of(E/Z)-1,3,3,3-tetrafluoro-N-(1,1,2,2,2-pentafluoroethyl)-2-[2,2,3,3-tetrafluoro-4-[(E/Z)-2-fluoro-2-[1,1,2,2,2-pentafluoroethyl(trifluoromethyl)amino]-1-(trifluoromethyl)vinyloxy]butoxy]-N-(trifluoromethyl)prop-1-en-1-amine

Following General Procedure B,(E/Z)-1,2,3,3,3-pentafluoro-N-(1,1,2,2,2-pentafluoroethyl)-N-(trifluoromethyl)prop-1-en-1-amine(3 equiv., 6.01 mmol, 2.0 g), KOH (2.2 equiv, 4.40 mmol, 247 mg),2,2,3,3-tetrafluorobutane-1,4-diol (1.0 equiv., 2.00 mmol., 0.324 g)were reacted in acetonitrile (4 mL). A small amount of Aliquat 336(N-Methyl-N,N-dioctan-1-ammonium chloride, 0.15 mmol, 0.12g) was alsocharged to the reaction mixture as a phase transfer catalyst tofacilitate the biphasic reaction. Analysis of the lower insolublefluorochemical phase by GC and GC/MS indicates that 100% of the startingdiol reagent was consumed. The yield of the desired difunctionalHFE-Olefin was 77.95% as a mixture of E/Z isomers, based on limitingreagent.

Example 25 Preparation of 1,3,3,3-tetrafluoro-2-methoxy-N,N-bis(trifluoromethyl)prop-1-en-1-amine

1,2,3,3,3 -pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine wasprepared by reaction of2-[[bis(trifluoromethyl)amino]-difluoro-methyl]-2,3,3,3-tetrafluoro-propanoylfluoride with anhydrous potassium carbonate in a 2 liter stainless steelnon-stirred reactor equipped with inlet and outlet ports. Vacuum ovendried potassium carbonate (2500 grams, 18.09 moles) was charged to thereactor and the reactor was heated to 220C.2-[[bis(trifluoromethyl)amino]-difluoro-methyl]-2,3,3,3-tetrafluoro-propanoylfluoride (1274.5 grams, 83.0% purity, 3.0 moles) made by Simonselectrochemical fluorination of methyl3-(dimethylamino)-2-methyl-propanoate was added through a dip tube at arate of 100 ml/hour. The gas from the reactor was collected in a dry icecooled receiver.1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine (935.9grams, 65.2% purity, 2.2 moles) was produced for a molar yield of 71.1%.The 1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine wasfurther purified by fractional distillation to a purity of 99.0%. Thestructure was confirmed by gc/ms.

1,2,3,3,3 -pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine (159grams, 99.0% pure, 0.55 moles), 45% aqueous KOH (83.2 grams, 0.67 moles)and Aliquat 336 (1 gram, 2.5 millimoles) were charged to 600 mlstainless steel Parr reactor equipped with stirrer, cooling coil andheating mantle. Methanol (19.6 grams, 0.61 moles) was added in threealiquots to the reactor over a one hour period. The temperature wasraised to 50 C, held two hours and then cooled to 35 C and stirred 16hours. A sample analyzed by gas chromatography showed 37.8% remaining1,2,3,3,3-pentafluoro-N,N-bis(trifluoromethyl)prop-1-en-1-amine.Acetonitrile (40 grams, 0.97 moles) was added to the reactor and thereactor was stirred at 50 C an additional 16 hours. The reactor wascooled to room temperature and the contents were washed three times withwater to provide 1,3,3,3-tetrafluoro-2-methoxy-N,N-bis(trifluoromethyl)prop-1-en-1-amine (122.8grams, 93.3% pure, 0.39 moles). The material was further purified byfractional distillation to a 99.3% pure mixture of cis and transisomers. The structure and purity were confirmed by gc/ms and F-NMR. Theboiling point is about 78° C.

Other embodiments of the invention are within the scope of the appendedclaims.

1. A hydrofluoroether compound represented by the following generalformula (I):

wherein, (i) Rf₃ is F, Rf₄ is CF₃, and Rf₁ and Rf₂ are independentlyperfluoroalkyl groups (a) having 1 to 2 carbon atoms and optionallycomprising at least one catenated heteroatom, or (b) that are bondedtogether to form a ring structure having 4-8 carbon atoms and optionallycomprising one or more catenated heteroatoms; or (ii) Rf₃ is CF₃, Rf₄ isF, and Rf₁ and Rf₂ are independently perfluoroalkyl groups (a) having 1to 8 carbon atoms and optionally comprising at least one catenatedheteroatom, or (b) that are bonded together to form a ring structurehaving 4 to 8 carbon atoms and optionally comprising one or morecatenated heteroatoms; and wherein Rfh is a linear, branched, or cyclicalkyl or fluoroalkyl group of from 1 to 10 carbon atoms that may besaturated or unsaturated and optionally comprises one or more catenatedheteroatoms.
 2. (canceled)
 3. A working fluid comprising ahydrofluoroether compound according to claim 1, wherein thehydrofluoroether compound is present in the working fluid at an amountof at least 50% by weight based on the total weight of the workingfluid.
 4. An apparatus for heat transfer comprising: a device; and amechanism for transferring heat to or from the device, the mechanismcomprising a heat transfer fluid that comprises a hydrofluoroethercompound according to claim
 1. 5. An apparatus for heat transferaccording to claim 4, wherein the device is selected from amicroprocessor, a semiconductor wafer used to manufacture asemiconductor device, a power control semiconductor, an electrochemicalcell, an electrical distribution switch gear, a power transformer, acircuit board, a multi-chip module, a packaged or unpackagedsemiconductor device, a fuel cell, and a laser.
 6. An apparatusaccording to claim 1, wherein the mechanism for transferring heat is acomponent in a system for maintaining a temperature or temperature rangeof an electronic device.
 7. A method of transferring heat comprising:providing a device; and transferring heat to or from the device using aheat transfer fluid that comprises a hydrofluoroether compound accordingto claim 1.